Polymer Chemistry Course, KTE 080, 2016 Patric Jannasch

————————————————————————————————

Laboratory procedures in
polymer chemistry

Polymer & Materials Chemistry

1. Free Radical Bulk Polymerization of Styrene

This protocol describes the bulk polymerization of styrene at 60 oC using 2,2´-

azobisisobutyronitril (AIBN) as an initiator. The monomer styrene first has to be purified before
it can be used. The purification is performed in order to remove inhibitors and impurities, which
can have a detrimental effect on the reaction. Styrene is purified by passing the monomer
through a column of activated basic aluminum oxide and by this treatment the inhibitors and
impurities are adsorbed. The styrene used in this laboratory experiment has already been purified
in this way, and has then been kept in a refrigerator to prevent thermal auto-initiation of the
monomer.

In total 8 mL of the desired mixtures of initiator and styrene and pure styrene are added to
reaction test tubes provided with glass stopcocks. A typical initiator concentration is around 1-8
g/L. The test tubes are shaken in order to properly homogenize the mixtures. Next, the tubes
with the glass stopcock are secured with springs. In order to purge (remove) the oxygen, which
will otherwise interfere with the polymerization, the tubes are evacuated using a vacuum
connection, and are then filled with pure nitrogen gas. This process is repeated three more times
to make sure that all the oxygen has been removed.

The polymerization reactions are performed in a heated water bath at 60 C for 2 hours. Note
the exact reaction time in seconds! After 2 hours the polymerization is stopped by immersing
the test tubes in an ice bath. The contents in the tubes are dissolved in 40 mL of toluene and the
different polymers are then precipitated by adding the solutions slowly, drop-by-drop, into 400
mL of methanol under vigorous stirring. It is very important that the solution is added drop-
wise slowly to the methanol so that a fine polymer precipitate is formed! Styrene is soluble in
methanol, while polystyrene is not. If the solution is added too quickly, monomeric styrene will
be captured in the polystyrene, which will lead to the formation of a monomer-swollen lump of
polymer, which in turn will cause much trouble in the next step. In order to obtain an appropriate
drop rate, a separation funnel should be used. The precipitate is first collected by filtering off the
precipitate using a glass filter crucible (weighed) and thoroughly washed with methanol and after
that dried in an oven at 50C until a constant weight is achieved. Note the final weight of the
samples. The dried samples are placed in marked vials and are kept for further analysis.

Polymer solutions for analysis by size-exclusion chromatography should be prepared at least 24

hours prior to the analysis.

1
2. Free Radical Copolymerization of Styrene and Butyl
Methacrylate

This protocol describes the bulk copolymerization of styrene and butyl methacrylate at 60 oC
using 2,2´-azobisisobutyronitril (AIBN) as an initiator. The monomers first have to be purified
before they can be used. The purification is performed in order to remove inhibitors and
impurities, which can have a detrimental effect on the reaction. The monomers are purified by
passing them through columns of activated basic aluminum oxide and by this treatment the
inhibitors and impurities are adsorbed. The monomers used in this laboratory experiment have
already been purified in this way, and have then been kept in a refrigerator to prevent thermal
auto-initiation.

In total 8 mL of the desired mixtures of initiator, butyl methacrylate, and styrene are added to
marked reaction test tubes provided with glass stopcocks. It is also suitable to homopolymerize
styrene in one of the tubes. The initiator concentration should be kept constant in these
experiments, and a suitable concentration is around 4 g/L. The test tubes are shaken in order to
properly homogenize the mixtures. Next, the tubes with the glass stopcock are secured with
springs. In order to purge (remove) the oxygen, which will otherwise interfere with the
polymerization, the tubes are evacuated using a vacuum connection, and are then filled with pure
nitrogen gas. This process is repeated three more times to make sure that all the oxygen has been
removed.

The polymerization reactions are performed in a heated water bath at 60 C for 2 hours. Note
the exact reaction time in seconds! After 2 hours the polymerization is stopped by immersing
the test tubes in an ice bath. The contents in the tubes are dissolved in 40 mL of toluene and the
different polymers are then precipitated by adding the solutions slowly, drop-by-drop, into 400
mL of methanol under vigorous stirring. It is very important that the solution is added drop-
wise slowly to the methanol so that a fine polymer precipitate is formed! The monomers are
soluble in methanol, while the polymers are not. If the solution is added too quickly, the
monomers will be captured in the polymers, which will lead to the formation of a monomer-
swollen lump of polymer, which in turn will cause much trouble in the next step. Copolymers
rich in butul methacrylate are more liable to form monomer-swollen lumps, and cooling the
methanol with ice might be necessary. In order to obtain an appropriate drop rate, a separation
funnel should be used. The precipitate is first collected by filtering off the precipitate using a glass
filter crucible (weighed) and thoroughly washed with methanol and after that dried in an oven at
50C until a constant weight is achieved. Note the final weight of the samples. The dried samples
are placed in marked vials and are kept for further analysis.

2
3. Condensation Polymerization to Prepare an Unsaturated
Polyester

The following protocol describes a condensation polymerization to produce an unsaturated linear

aliphatic polyester through a reaction between equimolar amounts of maleic acid, and 1,4-
butanediol using a strong acid as catalyst. The polymerization will be performed in a five-neck
glass reactor setup equipped with an electrical heater, a mechanical stirrer, a nitrogen gas inlet, a
thermometer, a water trap, and a condenser.

Add 0.5 mol 1,4-butanediol, 0.5 mol maleic acid, and p-toluene sulfonic acid (1.0-1.5 weight %) to
the reaction vessel. The catalyst should be weighed using an analytic balance since the exact mass
must be known in order to be able to calculate the average degree of polymerization of the
product after titration with KOH. Next, add 50 mL of toluene to the reaction mixture and close
the reactor. Fill the water trap with water up to the first line of the scale and then fill the rest of
the water trap with toluene. Start slowly the nitrogen flow and the stirrer, and start to heat the
reaction vessel until the toluene begins to boil. The reaction temperature, given by the boiling
point of toluene, will be between 100-110 °C. The reaction can continuously be followed by
measuring of the amount of water produced. Note the amount of water every second minute
until the conversion has reached at least 97-98% (what is the maximum amount of water
produced?). Quickly extract small samples from the reaction mixture at approx. 20, 40, 60, and
80% for the subsequent analysis by infrared spectroscopy. The toluene should be evaporated
from the samples before the analysis.

When the reaction mixture has cooled down, the concentration of carboxylic groups is
determined the following way: extract three 1 g (note the exact weight) liquid samples of the final
reaction mixture. Next, weigh the samples in E-flasks on an analytic balance. Dissolve the
samples in 20 ml acetone and titrate with 0.1 M alcoholic KOH using phenolphftalein as
indicator. Titrate also a blind sample of 20 ml acetone to ensure that the acetone does not
consume any KOH. Do not forget to correct for the p-toluene sulfonic acid when calculating the
concentration of acid groups!

3
4. Procedure for Measurement of Molecular weights and Molecular
Weight Distributions using Size-Exclusion Chromatography (SEC)

This protocol describes the analysis of chain lengths of polymers by SEC using conventional
calibration. This technique is applicable to a wide variety of polymers, of both low and high
molecular weights, dissolved in solvents of varying polarity. The selection of column type,
column pore size, solvent, and temperature must be appropriately made for each polymer. The
setup available comprises of:

 A Viscotek VE 1122 delivery system (1 mL chloroform per minute)

 A dual detector (refractive index/viscosity) model 250 from Viscotek equipped with the
TriSec® software
 A three-column package (Shodex SEC KF-805, 804 and 802.5) coupled in series
 A degassed solvent reservoir of chloroform solvent under a blanket of nitrogen.

You also have available 0.45 m Acrodisc® CR PTFE filters to remove particles, etc, from your
samples, and a 500-L syringe to inject the samples.

The polymer samples to be analyzed should be prepared at least 24 hours before analysis as
follows. Accurately weigh about 40-50 mg of the polymer into a 10 mL volumetric flask. Take
note of the exact weight. Add 6-7 mL of chloroform solvent to the volumetric flask using a clean
and dry pipette and close the flask. Let the polymer to dissolve overnight.

On the day of the SEC experiment, add chloroform up to the mark of the volumetric flask. Be
sure to shake the flasks several times to obtain homogeneous solutions. Label and uncap an
appropriate number of clean SEC vials. Rinse a 10-mL syringe and plunger twice with pure
chloroform. Next, place a 0.45 m Acrodisc® CR PTFE filter onto the tip of the syringe. Extract
the sample solution into the syringe. Insert the plunger and press until liquid passes through the
filter into the vial. Immediately cap the vials containing filtered sample. Finally, rinse the syringe
with the filter twice between each sample using chloroform.

To launch an experiment, use the following procedure:

- Open the programme “Data Acquisition”
- To set-up an experiment, go first to “System File > System set-up”. There, select the
correct group number in the ‘operator’ field. No other change should be made. Once you
are in “System File > Data Acq Direcotry”, check that you are in the following directory
“c:\gpc2005\lab”. Finally, you need to enter a run queue by clicking on “New…” in the
Run queue menu. There, type in the name of the sample that you will run. The file name
has to start with “gr” and your group number. It is a good idea to enter all the names of the
samples that will be run during the day to speed up the work (each sample being
alternatively from one or the other group).
- To launch the first experiment in the queue, click on “Start Acquisition” in the menu
Acquisition. A message “Waiting for trigger” will appear. The run will not start before the
trigger on the Data Manager is pushed. The trigger has to be pushed at the same time that
the sample is injected into the system.

Before injecting the sample, make sure that the temperature of the detectors is stabilized and that
the SEC set-up is not recycling the eluent.
4
To inject the sample in the system, use the following procedure:
- Using the 500 L syringe, take up to 450 L of your previously filtered sample. Make sure
that no air bubbles are present in the syringe. Next, place the syringe into the injector in the
LOAD position and inject your entire sample (the excess is collected with a beaker).
- While keeping the syringe in the injector, turn the injector to the INJECT position and
push the trigger of the Data Manager at the same time.
- Take out the syringe and rinse it three times with previously filtered chloroform.

At the end of the experiment, the next sample name in the queue list is loaded and the message
waiting for trigger will appear. Follow the same procedure to run the next sample.

Print the chromatogram after analyzing your first sample. You will then be given a chromatogram
of narrow standards with known molecular weights to prepare the calibration curve.
- Read the retention volume, Vr, for each of the narrow distribution polymer standards.
- Using the retention volumes, Vr, for the narrow distribution polymers and their molecular
weight, M, a calibration curve is constructed with log M versus Ve.
- Use the chromatogram of the polymer sample with unknown molecular weight to calculate
its Mn, Mw, and Mw/Mn. Please note that the amount of polymer at a specific Ve, or
corresponding molecular weight, is proportional to the height of the curve, Hi, at this
specific Ve:
- Hi ~ ni  Mi, where ni is the moles of the ith polymer and Mi is the molecular weight of that
polymer. A sufficient number of divisions should be taken to have a good accuracy.

The interpretation of the all the chromatograms will then also be carried out using the
programme “Conventional calibration”. Please refer to the manual for more information.

5
5. Structural Analysis of Polymers by Fourier Transform Infrared
(FTIR) Spectroscopy

FTIR spectroscopy may be used to determine if any characteristic absorption peaks appear or
disappear in the spectra, or if the relative intensities between two peaks change, for example,
during a polymerization. If the polymers to be analyzed are flowing melts at room-temperature,
spectra can be measured in transmission mode with the polymer spread out on a KBr tablet.
Make sure that the sample is properly dried before analysis. First, a ca. 0.5-1 mm thick tablet is
prepared by compressing a suitable amount of KBr powder for ca. 3 min. The tablet is gently
taken out of the mold. Next, a very thin film of the polymer is formed by first placing a small
droplet of the polymer melt on top of the tablet, and then scraping off the excess polymer with a
razor blade. The sample is now ready for analysis.

If the polymers solid at room-temperature, spectra can be measured in transmission mode with
the polymer in the form of a 10-50 micrometer thick films. An appropriate amount of polymer is
first dissolved in a suitable solvent. The solution is poured into a Petri dish. After evaporation of
the solvent, the polymer films are carefully dried under vacuum at 50 °C. Alternatively, a small
amount of carefully dried polymer precipitate is ground together with KBr powder. Subsequently,
a ca. 0.5-1 mm thick tablet is prepared by compression. The tablet is gently taken out of the mold
and is ready for analysis.

Make sure that the settings of the spectrometer are correct. You should measure spectra in the
range 400-4000 cm-1 in transmission mode. The results should be presented as absorption
spectra. Designate your recorded spectra so that you can easily identify it afterwards. In order to
subtract the contributions from oxygen, carbon dioxide, etc, from the atmosphere, a background
spectrum is first recorded. The same background spectrum is then used for all the subsequent
analyses. The lid of the spectrometer is opened for a short time to let in air. Make sure that there
is no sample in the sample holder. Gently close the lid. After waiting for 15 min., the background
spectrum is recorded. Now place the sample in the sample holder and place it in the
spectrometer. Wait 15 min. and then record the spectrum. The spectrum is directly visible on the
screen after the measurement is finished. Try to identify as many of the peaks and bands in the
spectra as possible using tables and charts of the absorption wavenumbers of known chemical
entities.